Hydrocarbon conversion process



Aug. 12, 1952 s. c. EASTWOOD HYDROCARBON CONVERSION PROCESS Filed March10, 1949 FLUE as our 22 W Lu] T L HI HEATER I 24 0001.51? 5 HIM. l/V 2/23 A/fifi r /4 FLUID 11v STEAM STEAM 5 SEAL CHAMBER SEAL v 55 cmuam-REDUCED 29 it" anuos FEED 30 5 Sheets-Sheet 1 F/G. I

aorivsron HEATER GATAL YT/C CRACK/N6 SYSTEM 1 CRACKED PRODUCT OUTINVENTOR. 5H. VA/VDER 6. EASTWOOD AGA/T 0R ATTORNEY Aug. 12, 1952 s. c.EASTWOOD HYDROCARBON CONVERSION PROCESS 5 Sheets-Sheet 2 FIG. 2

Filed March 10, 1949 COOLE/V 0 D T 5 E 0 M 0 5 WM MN /V E 9 U YL R E NA/PT L/ o N T F S K T a A0 NM R R 6T WE m m r R A al E f w 0 m T m v r N.v! M E 3 f m w w 6 w A o R M [M m J Mu r 07 8 Aug. 12, 1952 s, c,EASTWOOD 2,606,861

HYDROCARBON CONVERSION PROCESS Filed March 10, 1949 3 Sheetg-Sheet 3 775 F/POM warm 4 STE/7M 197 INVENTOR. f/Lkfl/VDEI? (3 457 W001) PatentedAug. 12,. 1952 I 2,606,861 HYDROCARBON ooNvERsioN PRQCESS- Sylvander C.Eastwood, Woodbury, N. J .,.assignor to Socony-Vacuum Oil Company,Incorporated, a corporation of New York 7 Application March 10, 1949,Serial No. 80,583

This invention pertains to the conversion of high boiling hydrocarbonstovaluable lower boiling products. It is particularly concerned with aprocess for the cracking conversion in the presence of solid contactmass materials of high boiling liquid petroleum fractions which undergothermal decomposition below temperatures at which they will vaporize.

It is well known that vaporized petroleum gas oils and the like may beconverted to lower boiling products containing high antiknock-gasolineby contacting the gas oil with adsorbent catalysts at temperatures ofthe order of about'8 F. and upwards and pressures usually of the orderof 5 to .100 pounds per square inchgauge. It is also known to similarlyconvert higher boiling petroleum fractions which exist in the liquidphase under the cracking conditions. However, in the latter case, theamount of coky material deposited on the catalyst during the crackingreaction is very high, particularly in the case of stocks having highcarbon residues such as petroleum residuums. In many cases the amount ofcoke deposit on the catalyst, which must be removed by burning in orderto maintain the catalyst activity is so high as to render the catalyticcracking of petroleum residue charges economically unfeasible. It isusually the practice to subject such petroleum residuums to apreliminary coking, tar separation or viscosity reducing treatment priorto use as a catalytic cracking charge stock. Often even in theseoperations, the gasiform stream from the coking vessel, for examplecontains substantial amounts of entrained liquid hydrocarbons having avery high carbon residue content. These streams cause serious coking onthe walls of the coking vessel near the gas outlets and in the transferlines leaving the coking unit and also in any heating furnace throughwhich they may pass prior to introduction into a catalytic crackingreactor. Also, the entrained liquid in the gasiform stream from thecoking unit may result in undesirable heavy coke deposits on thecracking catalyst thereby largely defeating the purpose of the coking ortar separation operation.

It is a major object of this invention to provide an improved processwhereby high boiling liquid petroleum fractions may be converted to highantiknock gasolines while avoiding the above mentioned difficulties.

Another object of this invention is the provision of an improved processfor conducting coking conversions of petroleum residuums to providelower boiling vaporizable products having low carbon residue contents.

11 Claims. (01. 196-52) 2 ,Aspecific object is the provisionof a ,novelcontinuous .processfor pyrolytically and catalytically, convertingpetroleum residuums and the like to gasoline containing productsin thepresence of suitable solid contact materials. These and other objects ofthis invention will become apparent from the following descriptionthereof.

This invention inits preferred form involves a method wherein the highboiling liquid hydrocarbon charge, for example apetroleum residuum isintroduced into the lower section. of a compact column of granularinertsheat carrying material to become converted pyrolytically to agasiform intermediate product which may contain small amounts ofentrained non-vaporized liquid hydrocarbons. The intermediate product isthen passed upwardly through the column until it contacts coolerheatcarrying material'by which it is quenchedto a temperature at whichthe pyrolytic reaction is substantially inhibited and the entrainedliquid is deposited'onto the heat carrying material. In some operations,a small percentage of the intermediate product may be condensed and alsodeposited u'ponthe contact material. The deposited liquid subsequentlybreaks down to cokeand gasiform product in the lower portion of thecolumn. The cooled gasiform intermediate product substantially free ofentrained liquid hydrocarbons is then heated toa suitable catalyticcracking temperature and passed into contact with a suitable adsorbentcatalyst to. effect its conversion to a product containing highantiknock gasoline. A stream of heated inert heat carrying material ispassed from a separate heater into the lower section of the column tosupply the heat required for the pyrolytic conversion of the liquidhydrocarbon charge. A second stream of the same heat carrying materialis supplied to the column at a higher level than the first stream and at.a lower ,temperature so as to effect the quenching of the intermediatereaction product. According to one form of this invention, a thirdstream of heat carrying material is supplied to thecolumn at a stillhigher level and at a temperature interme-v diate those of the first andsecond streams to efiect heating by direct heat exchange .of thequenched intermediate product to the catalytic cracking temperature.Used heat carrying material is withdrawn from the bottom of the columnto cause downward movement of the granular material in the column.

The inert granular material employed in the process of this inventionshould be .a solidmaterial having a relatively low orsubstantially nocatalytic cracking activity, a high heat absorption capacity and itshould be capable of withstanding high temperatures of the order of 1500F. without severe breakage, cracking or attrition. The material may benon-porous, for example metallic pieces or balls. Preferably however,the solid material should be porous, for example natural clays whichhave become deactivated so as to have a very low activity as a crackingcatalyst. Other materials which may be employed are pumice, mullite,fused alumina, silica, etc. A preferred heat carrying material isgranular petroleum coke. The granular material may range in size fromabout 100 mesh Tyler up to about one inch in diameter and preferably ofthe order of one-eighth to one-quarter inch diameter. The term granularis employed herein in a broad sense as including solids in variousshapes and forms such as pellets, tablets, spheres and irregular shapedparticles.

The catalyst employed for the final catalytic cracking step maypartakeof the nature of natural or treated clays, bauxites and the like orsynthetic associations of silica, alumina, magnesia or silica andalumina or silica and magnesia to which other metallic oxidesv may beadded for special purposes- The catalyst may be in the form of a powderin which event it may be maintained in suspension in the reaction zone.On the other hand, the catalyst may preferably be in the form ofgranular particles having average diameters within the range about 4 to100 mesh Tylerand preferably 4 to 20 mesh.

The invention may be more readily understood by reference to theattached drawings of which Figure 1 is an elevational View, partially insection, of one form of an arrangement for conducting the invention;Figure 2 is a similar View of a preferred form of the invention andFigure 3 is an elevational view, partially in section, of a modificationof part of the arrangement shown in Figure 2. All of these drawings arehighly diagrammatic in form.

Turning now to Figure 1. there is shown a vertical vessel H] which maybe of any convenient cross sectional shape. An outlet conduit H forsolid material withdrawal is provided at the bottom of vessel Hi and arow of liquid inlet pipes 12 connect into the lower section of thevessel. Suitable spray devices [3 are connected to the pipes l2. Liquidcharge may be supplied into pipes l2 and 18 respectively at their upperends and solid material outlets l9 and 20 respectively at their lowerends. An air inlet Hi connects into the lower section of heater i5 andmay communicate within the heater with gas distributors (not shown). Aflue gas outlet I i3 is providednear the top of the heater. Heattransfer tubes (not shown) may be provided within the heater and asuitable heat exchange fluid such as water or steam may be supplied tothese tubes via inlet 2[ and withdrawn therefrom via outlet 22. Anysuitable form of kiln adapted for burning of carbonaceous deposits fromsolid contact material may be substituted for the heater 15. In someoperations, the heating may be accomplished by means of combustion of afluid fuel within the heater in which event a mixture of air and fuelmay be supplied via inlet I l. The chamber [6 is adapted foreitheriheating or cooling the solid material depending on the particularoperating conditions involved. The solid material may be 4 cooled orheated within chamber l6 by direct contact with a suitable cooling orheating gas such as flue gas or steam supplied at 23 and withdrawn at24. Optionally, the cooling or heating may be accomplished by indirectheat transfer or by spraying a liquid onto the bed of solids in thecooling vessel.

In many operations the amount of contaminant deposit on the heatcarrying material may be satisfactorily regulated by burning on thecontaminant only from the material passed through heater l5. In otheroperations, it may be desirable to subject all of the circulating heatcarrying material to burning in which event a suitable kiln may beprovided in the line of pipe l3 prior to the exchanger l6.Alternatively, all of the material may be passed through vessel l5 afterwhich a portion is diverted to vessel [6 for temperature regulation.

The exchanger l6 communicates with the upper section of vessel in viaconduit 20 and branch pipes 26 which may be several in number. Theheater l5 communicates with a lower section of vessel [0 through conduit(9 and branch pipes 29. The ends of pipes 29 are provided with flaredmembers 30 to aid in the discharge of solids into the bed of heatcarrying material. A separate catalytic cracking system 21 is alsoprovided and is connected through conduit 3! and heater 32 and conduit33 to the upper part of vessel 10.

In operation, a substantially compact column Gil of granular heatcarrying material, for example petroleum coke, is maintained withinvessel i8. Coke is withdrawn from the bottom of vessel ID at a suitablerate controlled by valve t! on outlet 1 Prior to its withdrawal, thecoke is purged substantially free of gasiform hydrocarbons by means ofan inert purge gas such as steam or flue gas supplied through conduit'10. Part of the used coke bearing a coky deposit formed during thepyrolytic conversion reaction is passed via conveyor 36 and conduit l'linto heater [5 wherein it is heated by combustion of all or part of thecoky material deposited by the hydrocarbon conversion. In an exemplaryoperation, the coke may be heated from a convertor outlet temperature ofabout 800 F. to about 1100 F. at which temperature it is introduced intothe lower section of column 40. The rate of heated coke supply may becontrolled by means of slide valve 53 operated by rod 54 from a locationoutside the vessel or by other suitable means. A seal chamber 55 isprovided on the conduit 19 to prevent escape of hydrocarbons. Steam maybe supplied to the seal chamber via pipe 56. A petroleum residuum chargewhich may have been preheated to about 600 F. is introduced via conduit46 and pipes I2 and spray devices l3 into the column 49 at a levelshortly below the level of heated heat carrying material introduction.

The liquid oil is distributed uniformly onto the granular coke andheated thereby so as to effect pyrolytic cracking conversion to a lowerboiling intermediate product existing in the gaseous phase except for asmall amount of entrained non-vaporized liquid hydrocarbons. A cokycontaminant is deposited on the heat carrying material during thisreaction. The gasiform intermediate product and entrained liquidhydrocarbons pass upwardly through column 40 to be subjected toincreasingly higher temperatures until the level of spreaders 30 isreached. Thereafter, the intermediate product is quenched to asubstantially lower temperature by contact with the cooler coke suppliedfrom chamber [6 via conacoop'ci duit'ZB. The solidmaterial entering fromconduit :20 may be at atemperature of-about 850 F. for example..mainderof the use'd'material withdrawn from the bottom of vessel1-0-at800 F. and is heated to -850F. in exchanger -18. The rate andtemperature or the ratealone of introductionof the heat'carryingmaterial-onto the surface of=column 49 is.control1ed so as to cool theintermediate product to a temperature at which :thecokingor pyrolyticreaction is substantiallyinhibited, :and at which the entrainedliquidhydrocarbons are deposited on the heat carrying material. Ifdesired, the quench temperature maybe su'ificiently low to condense upto about percent .ofthe reaches in the coking zone. The liquid depositedon the heat carrying material is carried thereby down into the hotterzone below flared members so and is eventually cracked down to coke andlower boiling gasiform hydrocarbons. The term gasiform is used herein inabroad senseas covering material in' the gaseous phase under theparticularconditions of pressure and temperature at which it is presentregardless of what maybe the normal phase of the material under ordinaryatmospheric conditions. The quenched gasiform intermediate productiswithdrawn from the upper'section'of vessel fll via conduit 33 at atemperature of '850 F. for example and may lie-passed directly to thecatalytic cracking system 2! or heated first to about. 900 9'50Fxandthenpa'ssed to the catalyst reactor. The intermediate ;prodnot isconverted in the catalyst reactor to a "lower boiling product containinghigh antiknock gasoline. Since theentrained liquidhydrocarbons, whichhave a high residual carbon content are left behind in the vessel 19,-the conversion of the petroleum residuum to high anti-knock gasolineis accomplished without -;incurring excessively high coke :deposits onthecatalyst, Also, since the entrained high carbonresidue liquid hasbeen removed in that portion of vessel .19 wherein the granular heatcarrying material is flowing, the deposition of coke on the walls of-the-vessel near the outlet and in the transfer line 33 isavoided. Whenthe catalytic cracking system is not inoper ation the intermediateproduct from vessel it) may be withdrawn to storage viaconduit- 89. Theused heat carrying material is conveyed by a suitable conveyor .36 orgas lift to a level above chambers l5 and I6 and then :passes in part toeach stream as controlled by valves on conduits Hand 1 8. When amaterialother'than'petroleum coke is employed-as the heatcarrying-material; the amount of carbonaceous material thereon should bemaintained at-a low constant value by burning with a combustionsupporting *gas in heater [5, and if necessary, inan auxiliary 'kilninserted before chamber It. .If the heat-transfer materialis petroleumcoke, only so much of the coke deposit thereon need be burned off aswill meet theheat requirements or" thecyclic system. If the amount ofcoke in the system builds-up it may be withdrawn as a by-product viaconduit 28%. Inert gas seal zones 55 and 55' are provided on conduits 59and to prevent escape of This material constitutes the 're-.

\6 hydrocarbons from vessel 13 into the chambers l5 and 16. It isnotessential thatchambers l5 and I6 be positioned above thevessel [0 aslong as'a suitable means isprovided for solidsttrans'fer fromc'hambersBrand it to the proper levels'in vessel-l0. 7 In most operations thedesired quench temperature is below'that required for the-catalyticcracking reaction and in such operations itis preferable to employ thearrangement shown in Figure '2 of the drawings- In Figures 1 and 2,equivalent elementsbear similar numerals and need not be furtherdescribed. In thearran'gement shown in Figure 2 the heated heat carryingmaterial fromheateriifi passes via conduit 88' into-a seal chamber 8!provided in the upper section of vessel'82. Part of the heated solidmaterial passes via tubes 84 onto the surface of column 40 and theremainder passes via' tubes '85 into the lower section of the column.Slide valves 36 are provided for rate control. Cooled solid materialpasses from cooler it via conduit 81 and tubes!!!) into the column at anintermediate level. Flared members 89 and Sll are provided on the lowerends of tubes "85 and tubes 88 respectively. Baflles we may be providedbelow flared-mem here 90 to insure uniform mixing of the solid materialfrom tubes 88 with the solids flowing down from the upper portion of thecolumn.

In atypical operation heated solid material may be supplied throughtubes 85 and 84 at about 7 1200"v F. Cooled solid material may enter thecolumn from tubes .88 at 700 F. Liquid hydrocarbon charge may be"supplied from conduit 9!, pipes Bland nozzles 93 into the columnbe'low'the level of hot heat carrying material introduction. The liquidcharge is convertedin-theicoking zone A by means of the heat supplied bythe heat carrying material. The intermediate conversion productscarrying entrained non-vaporized liquid hydrocarbons pass up through thecolumn to be cooled inthe quench zone B which lies between the levels offlared members '89 and 90. The quenched vapors at'about '750.F.thenenter the preheating zone A whichoccupies that portion of the columnabove flared members :90. In the preheating zone the vapors are heatedto a suitable catalytic cracking temperature, for examplev 850 F. andare then disengaged from the-column surface and passed via-conduit 33 tothe catalytic reactor 55. The rate of supply of heated heatcarryingmaterial to the preheating zone maybe controlled by means ofplug valves 95 :to provide thedesired vapor-outlet temperature;'Tn'erate of hot solid material supply to the coking zone may-becontrolled by slide valves '86 an'd the :cool solid supply to the'quenchzone may be controlled by valve 19!. Downward movement 'of'the heatcarrying -material through all 'of theezones isaccomplished bywithdrawalof the usedheatcarrying material from the bottom of the vessel throughconduit 1 i. This causes the heat carrying material from the zone A tojoin that supplied from tubes 88 into zone B and the-material from zoneB joins that supplied from tubes- 85 into zoneC. A -preferred method 'ofoperation is to set the valves l9! and 86 so as to allow the properproportions and amounts of cool and heated solid material to enter zones.3 and C respectively and to set the valve -"4I on outlet H tojpermitwithdrawal via'conduit H of an amount of solid material which is inexcess of the total ofthe solids supplied via pipes 88 and 85 by anamount corresponding to the requirements ofzone A. :Pipes 84 then neednot be throttled so that they serve to control the column surface levelconstant. Uniform flow and purging of the granular solid material may beaccomplished by an orifice plate arrangement as shown in Figure 2. Thisarrangement is claimed and described in United States Patent 2,434,202issued January 6, 1948. The catalytic reactor95 may preferably be of themoving bed type which is described in United States Patent 2,419,507,issued to Simpson et al. on April 22, 1947. Adsorbent catalyst ingranular form passes downwardly through the reactor 95 and is contactedby the rising petroleum vapors which are converted to a gasolinecontaining product. The gasiform product is withdrawn via conduit I05.The form of the invention shown in Figure 2 offers several importantadvantages. It permits the preheating of the intermediate gasiformproduct to the cat alytic cracking temperature within the same vesseland column of solid material that is employed for the pyrolyticconversion, thereby eliminating the need for a separate furnace.Moreover, the heat required for the preheating is supplied from withinthe coking system by burning formed coke, thereby efiecting a savinginheating fuel requirements. In addition, the quenched stream from zoneB is heated to a level substantially above its dew point in zone Athereby eliminating the danger of heavy oil condensation in the upperpart of vessel 02 and in the transfer line 33. If there is any tendencyfor coke formation during the preheating step, it is deposited on theheat carrying material and not in the tubes of a preheating furnace. Asdiscussed above in connection with Figure 1, in some operations the heatcarrying material introduction via tubes 83 into the quench zone may beintroduced at a temperatwo slightly above that of the solid materialdischarged from the bottom of vessel 02 via conduit II. In suchoperations, the chamber It may be operated as a heater. Also, in someoperations the temperature of the used heat carrying material may beapproximately that desired for the quench zone in which case the chamberI8 may be employed purely as a surge hopper in the cyclic system.

In order to permit greater flexibility of control in the preheating zoneprovision may be made for separate control of the temperature of theheat carrying material supplied onto the column surface. Such anarrangement is shown in Figure 3 which shows a modified portion of thearrange'ment in Figure 2, the rest of the arrangement remaining thesame. In Figure 3, double supply chambers I01 and I are provided in theupper section of vessel '82 by means of horizontal partitions IM andI02. from heater I5 (shown in Figure 2) passes down through conduit 00which fits through partition IOI into the chamber I06 from which itpasses via tubes 85 to the pyrolytic conversion zone. A part of theheated heat carrying material is permitted to flow from conduit 80through pipes I I0 into chamber I01 above partition IOI. Conical valvesI09 mounted on slide rods III are provided to control the rate of solidmaterial flow from pipes I10. The rods III slide through bushings H2which should be gas tight. The temperature of the solid material inchamber I0! is controlled by admitting cooler material from an externalcooler via conduit 8! to I I I. If desired, a separate exchanger (notshown) may be provided in which the solid supply for the preheating zoneis regulated to the proper temperature level and then supplied intochamber Heated solid materialconduit I10 connects.

I0I' via conduits H2 and III. In this case, the pipes H0 may beeliminated. Cooled contact material passes from a cooler through pipe 81into the lower'portion of a distributing zone I22 defined between spacedhorizontal partitions [2| and I23. The contact material is deliveredinto the zone I22 from a confining cone I into which Cooled contactmaterial passes from zone I22*via a plurality of pipes I into'thef'surface of the column I40 in a lower portion of the vessel. -A gaswithdrawal space I4! is provided around the pipes I30 and above thecolumn I40. It will be noted that the hot contact material supply pipesextending down from partition I02 arepositioned laterally between pipesISO and terminate at a substantially lower level in the vessel thanpipes I30, thereby providing for a, quench zone in the upper portion ofthe column and a conversion zone therebelow. Liquid petroleum residuumis charged from manifold I52 and nozzle pipes I53 onto the column belowangle baffles I54 at a level below that of the hot contact materialsupply. The vapors resulting from the coking reaction pass up throughthe cooler material in the quench zone I where they are quenched toinhibit further reaction and to effect condensation on the contactmaterial of entrained liquid hydrocarbons. The quenched vapors pass fromthe gas space MI via by-pass pipe I53 into distributor troughs I54positioned in the bed I80 of contact material shortly above partitionI23. The reactant vapors are then heated to a temperature suitable foreffecting catalytic conversion thereof by means of the contact materialentering from zone I01 at a suitable controlled temperature. Preheatedvapors then pass via conduit I55 to the catalytic reactor. The contactmaterial from the preheating bed I00 passes via pipes I51 onto thesurface of column I40 at a temperature which is usually below that ofthe contact material supplied through pipes 85 but above that of thecooled material entering via pipes I30. Flow throttle cones I mounted onrods I6I which slide through bushings I62 are positioned below pipesI30. The cones may be raised or lowered by rotation of the eccentricsI85 mounted on shaft IE6 below the Y-shaped end of rods ISI. Slidevalves I62 operated from the back side of the unit similarly to valves86 of Figure 2 are mounted on pipes 05. By means of cone valves I60 andslide valves I62 the rate and relative proportion of heated and coolcontact material delivery to the column I40 may be controlled. Thevalves are set so that the total of these two streams is less than thetotal contact material wihdrawn from the bottom of the vessel. Thedifferential is automatically taken up by the contact material flowingthrough open pipes I5! from the preheating bed I80. It will be notedthat since the other two contact material streams are individuallycontrolled by throttle valves, the rate of contact material flow fromzone I01 onto the preheating bed I may be controlled by control of therate of solid withdrawal from the bottom of the vessel and at the sametime the stream from the zone I01 serves automatically to maintainconstant the surface levels of bed I80 and column I40. The escape ofhydrocarbons through the solid material feed pipes is prevented byintroduction of a seal gas such as steam or flue gas via pipes I95, I96and I91 at rates suflicient to maintain the inert gas pressure in thezones of its introduction slightly greater than the reactant pressure inthe. bed

I80 and column I40. u The particular operating conditionsto be employedin the process of this invention vary over a'wide range depending upontheoriginal charge stock, the heat carrying material andcatalystemployed and the desired severity of the pyrolytic "cracking reaction.In general, the operation W111 fall within the following approximateranges of temperature:

Contact Material Streams rin Ookin Zone Broad Range. FnteD g PreferredRange.

Broad Range. Preferred Range. Broad Range. Preferred Range. Broad Range.Preferred Range.

Broad Range. Preferred Range. Broad Range. Preferred Range.

e Entegng Quench Zone o Leaving Catalytic Reactor l.

Charge to Coking Zone Broad Range.

, Preferred Range.

Broad Range.

The temperatures given above for thequench zone inlet stream are thosefor operations when a preheating zone is not provided) thereabove. Whena preheating zone is provided the solid material inlet temperature tothequench zone 1 is somewhat lower than that given: in the above table,for example the preferred inlet temperature may be of the order0?;650-850 F. The pressure in the coking zone is usually of the order ofnearly atmospheric up to about-30 pounds per'square inch-gauge but mayrange up to about 200 pounds per square inch in some operations. Thetemperature ranges given above are for the low pressure operation; Thepressure in'the catalytic reactor is usually of the orderof 5-30 poundsper square inch but may in someinstances be substantially higher. Therelative rates of heat carrying material and reactant flow injthecoking, quench and preheating zones is purely a question .of thermalbalance, the heat carrying material being regulated in rate of flow andinlet temperature to carry substantially the entire heating or coolingload in the zone in question. In the catalytic reactor the reactantspace velocity may range from about 0.5'to'10.0 volumes of oil'charge'per hour (measured as a liquidat 60F.) per volume of'catalystein thereaction zone." The catalyst to oil ratio may vary from about 1 to partsof catalyst per part of oil charge per-hour by weight.

The specificexamples of operation and details of apparatus arrangementand process technique given hereinabove are intended as exemplary andshould not be construed as limiting the scope of this invention exceptasit may be limited by the following claims. 1 I claim: I

1. A method for.conversion-of-highboiling liquid hydrocarbons to lowerboiling ihydrocarbon products: which: comprises: maintaining asubstantiallyrcompact bed of granular solidheatcarrying material in anupright confined zone, withdrawing a stream of solid material from thelower section of said 'zone to cause downward movement of thesolidmaterial in saidbed, introducing high-boiling liquid hydrocarbons intosaid bed at an intermediate level. alongits length to' contact-said-heatcarrying material and to effect a partial I conversion ofsaid, liquid hydrocarbons to a gasiform product. containing lowerboiling hydrocarbonsand a small amount of entrained unvaporizecl liquidhydrocarbons and with th deposition 7 -of a carbonaceous coky materialon the heat carrying material, said liquid hydrocarbons being introducedat a temperature below that required for 1 products.

; boiling .version thereof to lower ing products.

some but only a small portion of said gasiform product, passing saidga'siform product containing entrained liquid upwardly through said bedto contact said cooler solid material whereby the 'conversion reactionis substantially inhibited and a small portion of the gasiform productis condensed and deposited upon the solid material along'with saidentrained liquid, withdrawing the gas'iforrn product from the uppersection of said zone and passing it into contact with a finely dividedadsorbent catalyst under conditions of temperature and pressure suitablefor effecting further conversion to gasiformfgasoline containing 2. Amethod for catalytically converting high petroleumiractions containingconstituen'ts which decompose belowtheir boilin temperatures whichcomprises, maintaining a substantially compact column of granular heatcarrying material in a confined upright zone, introducing a high boilingpetroleum fractionas aliquid into said column at an intermediate levelalong its length to-effect thermal coking 'of said petroleum fraction toa gasiform product containing a small amount of relatively high boilingentrained liquid and to a coky deposit on the heat carrying material,introducing a first stream of heated inert heat carrying material intosaid column shortly above the level ofliquid hydrocarbon introduction ata temperature above that of said petroleum fraction and above theaverage coking temperature and sufficiently high to supply the heatrequired for the cokingreaction, introducing a second stream ofsubstantially, cooler inertheat carrying material onto the surfaceor"said column, said cooler heat carryingmaterial being at a temperature;above that at which most of said product will condense, withdrawing.used

heat carrying material from the bottom of said column to cause-downwardmovement of the heat carryingmaterial through said confined zone,

passing the gasiform product formed in said cokingreaction along withthe entrained high boiling liquidhydrocarbons upwardly within saidcolumn to contact progressively hotter heat carrying material until itreaches the level of the heated material introduction and then tocontact progressively cooler heat carrying material in the upperportionof said column whereby theentrained liquid hydrocarbons are leftbehind on the heat carrying material as'the gasi form products leave thesurface-of said column, and passing thegasiform products substantiallyfree of entrained liq- .uid hydrocarbons'into contact with a finelydivided catalyst tokeifect the-catalytic c'rackingconboiling gasolinecontain- 3. A method for conversion of petroleum residuums to highantiknock gasoline comprising, maintaining a substantially compactcolumn of granular, petroleum coke, in an elongated, confined zone,supplying, heated granular coke into said column at an intermediatelevel to maintain the column temperature below said level ofintroduction at a suitable range of coking temperatures below about1200" F., supplying granular cokeonto the surface of said column at atemperature substantially below that of the heated coke introduction andbelow about 1000 F., withdrawing used granular coke from the bottom ofsaid column, introducing petroleum residuum charge in the liquid phaseinto said column below the level of heated coke introduction to eifectcoking of said charge to lower boiling gasiform hydrocarbons, saidpetroleum charge being introduced at a temperature insufiicient toeffect its coking so that the heat required for the coking is suppliedby said granular coke passing the gasiform hydrocarbons upwardly throughsaid column along with a small amount of nonvaporized liquidhydrocarbons to contact first the heated coke and later the cooler cokein the upper section of said column, whereby the gasi-form product iscooled to a temperature substantially below the highest level to whichit was heated by said heated coke, whereby the entrained liquidhydrocarbons areideposited on said coke, withdrawing the gasiformproduct from said. column below the temperature required for itscatalytic cracking conversion temperature and heating it to saidcatalytic cracking conversion temperature which is above about 800 F.,passing the heated gasiform product into contact with a granularcracking catalyst to effect its further conversion to a high antiknockgasoline containing product and separating said gasoline containingproduct from said catalyst. I

4. A method for conversion of petroleum residuums to high antiknockgasoline comprising, maintaining a substantially compact column ofgranular, substantially inert heat carrying material in an elongated,confined zone, introducing petroleum residuum charge as a liquidrintothe lower portion of said column to effect coking thereof at a suitablerange of coking temperatures to provide a stream of lower boilinghydrocarbons in the gaseous phase in which is entrained somenon-vaporized liquid hydrocarbons, passing said stream upwardly into acooler and intermediate portion of said column wherein it is cooled bycontact with the heat carrying material to a quench temperature at whichthe coking reaction is substantially inhibited and the entrained liquidis deposited on the solid heat carrying material, said quenchtemperature being substantially below the highest temperature reached insaid lower portion of said column and being below the suitable catalyticcracking temperature, passing the cooled stream, substantially free ofentrained liquid up through an upper portion of said column whereinitstemperature is raised to a suitable temperature for its catalyticconversion which is below the maximum temperature reached by said streamin said lower portion of the column, withdrawing the heated stream fromsaid column and passing it into contact with a finely divided catalystto efiect its cracking conversion to a gasoline containing product in aseparate zone and effecting a separation of said product for the usedcracking catalyst, introducing a first portion of inert solid heatcarrying material into said column at a level shortly above 12 that ofthe liquid residuum charge and at a temperature substantially above theaverage coking temperature in said lower portion of said column,

introducing a second portion of said heat carrying material into saidcolumn at an intermediate level below its surface and above the level ofsaid first portion and at a quench temperature substantially below thatof said first portion, controlling the rate and temperature ofintroduction of said second portion of heat carrying material to effectthe quenchin of said stream of gasiform hydrocarbons as aforesaid,introducing a third portion of said heat carrying material onto thesurface of said column at a temperature substantially abovethat of saidsecond portion, controlling the rate of introduction of said thirdportion to effect heating of said .gasiform stream to said suitablecatalytic cracking conversion temperature and withdrawing said inertheat carrying material at a controlled rate from the bottom of saidcolumn.

5. A method for conversion of petroleum residuums to high antiknockgasoline comprising, maintaining a substantially compact column ofgranular substantially inert heat carrying material in an elongated,confined zone, introducing petroleum residuum charge as a liquid intothe lower portion of said column to effect coking thereof at a suitablerange of coking temperatures to provide a stream of lower boilinghydrocarbons in the gaseous phase in which is entrained somenon-vaporized liquid hydrocarbons, passing said stream upwardly into acooler and intermediate portion of said column wherein it is cooled bycontact with the heat carrying material to a quench temperature at whichthe coking reaction is substantially inhibited and the entrained liquidis deposited on the solid heat carrying material, said quenchtemperature bein substantially below the highest temperature reached in.said lower portion of said column and being below the suitablecatalytic cracking temperature, passing the cooled stream, substantiallyfree of entrained liquid up through an upper portion of said columnwherein its temperature is raised to a suitable temperature for itscatalytic conversion which is below the maximum temperature reached bysaid stream in said lower portion of the column, introducing a firstportion of inert solid heat carrying material into said column at alevel shortly above that of the liquid residuum charge and at atemperature substantially above the average coking temperature in saidlower portion of said column, introducing a second portion of said heatcarrying material into said column at an intermediate level below itssurface and above the level of said first portion and at a quenchtemperature substantially below that of said first portion controllingthe rate and temperature of introduction of said second portion of heatcarrying material to effect the quenching of said stream of gasiformhydrocarbons as aforesaid, introducing a third portion of said heatcarrying material onto the surface of said column at a temperaturesubstantially above that of said second portion, controlling the rate'ofintroduction of said third portion to effect heating of said gasiformstream to said suitable catalytic cracking conversion column,withdrawing used heat carrying material at a controlled rate from thebottom of said column, passing a part of the used heat carrying materialthrough a separate heat- 1 ing zone wherein it is heated to atemperature suitable for reuse, uti1izin ga part of the heated heatcarrying material to supply said first portion of heat carrying materialintroduced into said column, utilizing. the remainder of the heated heatcarrying material to supply said third por tion introduced onto saidcolumn, passing the remainder of the ,used heat carrying materialthrough a separate heat exchange zone wherein it is regulated to asuitable quench temperature and utilizing the latter heat carryingmaterial to supply said second portion introduced into said column,withdrawing the heated stream from said column and passing it intocontact with a finely divided catalyst to effect its cracking conversionto a gasoline containing product in a separate zone and efiecting aseparation of said product from the used cracking catalyst.

6. A method for conversion of petroleum residuums to high antiknockgasoline-comprising, maintaininga substantially compact column ofgranular, substantially inert heat carrying material in an elongated,confined zone, introducing petroleum residuum charge as a liquid intothe lower portion of said column to effect partial conversion andgasification thereof at an elevated temperature suitable for pyrolyticcracking of the residuum to form a stream of lower boiling gasiformhydrocarbons containing a small amount of entrained non-gasified liquidhydrocarbons, passing said stream upwardly into a cooler andintermediate portion of said column wherein it is cooled by contact withthe heat carrying material to a quench temperature at which thepyrolytic cracking reaction is substantially inhibited and a minorfraction of the stream is condensed and deposited on the solid heatcarrying material along with the liquid entrained from the lower portionof said column, said quench temperature beingsubstantially below thehighest temperature reached in said lower portion of said column andbeing below the suitable catalytic cracking temperature, passing thecooled stream, substantially free of entrained liquid up through anupper portion of said column wherein its temperature is raised to asuitable temperature for its catalytic conversion which is below themaximum temperaturereached by said stream in said lower portion of thecolumn, withdrawing the heated stream from said column and passing itinto contact with a finely divided catalyst to effect its crackingconversion to a gasoline containing product in a separate zone andeffecting a separation of said product from the used cracking catalyst,introducing a first portion of inert solid heat carrying material intosaid column at a level shortly above that of the liquid residuum chargeand at a temperature substantially above the average pyrolytic crackingtemperature in said lower portion of said column, introducing a secondportion of said heat carrying material onto the surface of said columnat a temperature at least equal to said suitable catalytic crackintemperature and substantially below that of said first portion of heatcarrying material, introducing a third portion of said heat carryingmaterial into said column at a level intermediate the levels ofintroduction of said first and second portions of heat carrying materialand at a quench temperature which is below that of said second portionbut insufiiciently,

low to condense most of said stream of lower boiling hydrocarbons formedin saidlower portion of said column, and

heat carrying material at acontrolled rate from the bottom of saidcolumn.

'7. A method for conversion of highiboiling liquid petroleum fractionsto a lower boiling gasowithdrawing said inert 14 linecontainingconversion product' comprising, maintaining a substantiallycompact column of granular heat carrying material of low catalyticactivity extending upwardly through a lowermost pyrolytic conversionzone, anintermediate quenching zone and an upper preheating zone,

withdrawing :heat carrying material from, the bottom of :said column tocause downward move existing mainly in the gaseous phase butcontainingsmall'amounts of non-vaporizedliquid hydrocarbonasubjectin a secondportion of the heat carrying material withdrawn frem-sai'd-celunmtocooling to effect reduction in its temperature to a level suitable-forsubstantially quenching the pyrolytic cracking reaction but above thatwhich would cause condensation of more than about 15 percent of saidintermediate product and introducing this latter-material into saidcolumn at an intermediate level corresponding to the upper section ofsaid quench zone," passing the gasiform intermediate product withentrained liquid up wardlyfrom said pyrolytic conversion zone intocontact with the cooler heat carryingmaterial in said quench zonewhereby the reaction is substantially inhibited'and the entrained liquidis deposited onto the heat carrying material, adjusting the temperatureof a third portion of the heat carrying material withdrawn from saidcolumnto a level intermediate that of said first and second portions andat least equal to a suitable temperature for the catalytic crackingconversion of said intermediate product and supplying said third portiononto the surface of said column which corresponds to the top of saidupper. heating zone, passing the quenched intermediate gasiformproductupwardly from said quench zone into contact with-the hotter heatcarrying material in said heating zone whereby it is heated to asuitable temperature for its catalytic cracking conversion and passingthe heated intermediate product into contact with a suitable finelydivided adsorbent cracking catalyst in a separate, confined zone toefiect its conversion to a gasoline containing product.

8. -A method for coking high boiling petroleum fractions to lower boilinproducts comprising, maintaining a substantially compact column ofgranular heat carrying material of low catalytic activityextendingthrough a lower coking zone and an upper quench zone,withdrawing heat carrying material from the bottom of said column terialtherein, whereby it undergoes coking to form a lower boiling gaseousproduct existing mainly in the gaseous phase but containing smallamounts of high-carbon-residue liquid hydrocarbons, subjecting a secondportion of the heat carrying material withdrawn from said column tocooling to effect reduction in its temperature to a level suitable forsubstantially quenching the coking reaction but above that which wouldcause condensation of more than about 15 percent of said lower boilingproduct and introducing this latter material into said column at a levelcorresponding to the upper section of said quench zone, passin the lowerboiling product with entrained liquid upwardly from said coking zoneinto contact with the cooler heat carrying material in said quench zonewhereby the reaction is substantially inhibited and the entrainedhighcarbon-residue liquid is deposited upon the heat carrying material,withdrawing said lower boiling product in gaseous form and substantiallyfree of entrained liquid hydrocarbons from the upper section of saidcolumn at a temperature above that at which more than 15 percent of theproduct condenses,

9. A method for conversion of petroleum residuums to high antiknockgasoline comprising, maintaining a substantially compact column ofgranular, substantially inert heat carrying material in an elongated,confined zone, introducing petroleum residuum charge as a liquid intothe lower portion of said column to eifect partial conversion andgasifioation thereof at an elevated temperature suitable for pyrolyticcracking of the residuum to form a stream of lower boiling gasiformhydrocarbons containing a small amount of entrained non-gasified liquidhydrocarbons, passing said stream upwardly into a cooler andintermediate portion of said column wherein it is cooled by contact withthe heat carrying material to a quench temperature at which thepyrolytic cracking reaction is substantially inhibited, said quenchtemperature being below a suitable catalytic cracking temperature,passing the cooled stream up through an upper portion of said columnwherein its temperature is raised to a level suitable for catalyticconversion of the hydrocarbons, withdrawing the heate stream from saidcolumn and passing it into contact with a suitable catalyst to effectits cracking conversion to a product containing high octane gasoline andeffecting separation of said product from the cracking catalyst,introducing a first portion of inert solid heat carrying material intoaid column at a level shortly above that of the liquid residuum chargeand at a temperature substantially above the average pyrolytic crackingtemperature in said lower portion of said column, introducing a secondportion of said heat carrying material onto the surface of said columnat a temperature at least equal to said suitable catalytic crackingtemperature and substantially below that of said first portion of heatcarrying material, introducing a third portion of said heat carryingmaterial into said column at a level intermediate the levels ofintroduction of said first and second portions of heat carrying materialand at a quench temperature which is below that of said second portionbut insufliciently low to condense most of said stream of lower boilinghydrocarbons formed in said lower portion of said column, controllingthe rate of introduction of the first and third portions of the heatcarrying material into said column to supply the heat for said py olyticreaction and to supply the cooling capacity for the product quenchingrespectively, withdrawing heat carrying material from the bottom of saidcolumn at a rate which is in excess of the total rate of supply of saidfirst and third portions by an amount approximately equal to therequired rate of supply of said second portion to effect the reactantpreheating and supplying said second portion onto the surface of saidcolumn at a rate adjusted to maintain constant the surface level of saidcolumn.

10. A method for efiecting high temperature conversions of high boilingpetroleum fractions comprising maintaining a substantially compactcolumn of granular heat carrying material in a confined upright zone,introducing a high boiling petroleum fraction as a liquid into saidcolumn at an intermediate level along its'length to effect thermal cokinof said petroleum fraction to a gasiform product containing a smallamount of relatively high boilin entrained liquid and to a coky depositon the heat carrying material, introducing a first stream of heatedinert heat carrying material into said column shortly above the level ofliquid hydrocarbon introduction at a temperature above the averagecoking temperature and at a rate positively controlled to effect upplyas sensible heat in the heat carrying material the heat required for thecoking reaction, introducing substantially cooler heat carrying materialinto said column at a higher level therein spaced substantially belowthe column surface, said cooler heat carrying material being at atemperature substantially below said coking temperature and the rate ofsaid cooler heat car ying material introduction being positivelycontrolled to efiect quenching of the gasiform product flowing up fromthe lower and hotter portion of said column and the deposition ofentrained liquid on the solid material, withdrawin heat carryingmaterial from the bottom of said'column at a rate substantially abovethe combined rates of introduction of said first and second streams,flowing by gravity a stream of heat carrying material existing at atemperature intermediate said first and second streams from an externalsupply zone down onto the surface of said column to maintain said columncontinuously replenished and to supply into the upper portion of saidcolumn sufficient heat to raise the temperature of the quenched gasiformproduct to a level intermediate the coking and quench temperatures andwithdrawing the reheated gasiform product from the upper portion of saidcolumn.

11. A method for coking high boiling petroleum fractions to lowerboiling products comprising, maintaining a substantially compact columnof granular heat carrying material of low catalytic activity extendingthrough a lower coking zone and an upper quench zone, withdrawing heatcarryin material from the lower section of said column to cause downwardmovement of the heat carrying material through all of said zones,supplying heat carrying material at a temperature suitable forsupporting the coking reaction and upplying it into said column at alevel corresponding to the upper portion of the coking zone, introducinga high boiling liquid petroleum fraction into said coking zone at atemperature below that of said heat carrying material and insufficientto provide the heat for said coking reaction to contact said heatcarrying material therein, whereby it undergoes coking to form a lowerboiling gaseous product existing mainly in the gaseous phase butcontaining small amounts of 17 high-carbon residue liquid hydrocarbons,introducing a second portion of solid heat carrying material into aidcolumn at a level corresponding to the upper section of said quench zoneat a temperature level suitable for substantially quenching the cokingreaction and also condensing a minor fraction of but not more than about15 percent of said lower boiling product, passing the lower boilingproduct with entrained liquid upwardly from said coking zone intocontact with the cooler heat carrying material in said quench zone,whereby the reaction is substantially inhibited and a minor fraction ofthe lower boiling product stream is condensed and deposited on the solidheat carrying material along with said entrained high-carbon-residueliquid, withdrawin the remaining lower 18 boiling product in gaseousform and substantially free of entrained liquid hydrocarbons from theupper section of said column at a temperature above that at which morethan 15 percent of the product condenses.

SYLVANDER C. EASTWOOD.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 7 2,348,699 Tuttle May 9, 19442,403,608 Payne et al July 9, 1946 2,466,005 Crowley Apr. 5, 19492,513,294 Eastwood et al July 4, 1950

1. A METHOD FOR CONVERSION OF HIGH BOILING LIQUID HYDROCARBONS TO LOWERBOILING HYDROCARBON PRODUCTS WHICH COMPRISES: MAINTAINING ASUBSTANTIALLY COMPACT BED OF GRANULAR SOLID HEAT CARRYING MATERIAL IN ANUPRIGHT CONFINED ZONE, WITHDRAWING A STREAM OF SOLID MATERIAL FROM THELOWER SECTION OF SAID ZONE TO CAUSE DOWNWARD MOVEMENT OF THE SOLIDMATERIAL IN SAID BED, INTRODUCING HIGH BOILING LIQUID HYDROCARBONS INTOSAID BED AT AN INTERMEDIATE LEVEL ALONG ITS LENGTH TO CONTACT SAID HEATCARRYING MATERIAL AND TO EFFECT A PARTIAL CONVERSION OF SAID LIQUIDHYDROCARBONS TO A GASIFORM PRODUCT CONTAINING LOWER BOILING HYDROCARBONSAND A SMALL AMOUNT OF ENTRAINED UNVAPORIZED LIQUID HYDROCARBONS AND WITHTHE DEPOSITION OF A CARBONACEOUS COKY MATERIAL ON THE HEAT CARRYINGMATERIAL, SAID LIQUID HYDROCARBONS BEING INTRODUCED AT A TEMPERATUREBELOW THAT REQUIRED FOR ITS PARTIAL CONVERSION, INTRODUCING HEATED SOLIDHEAT CARRYING MATERIAL INTO AN INTERMEDIATE PORTION OF SAID BED NEAR THELEVEL OF LIQUID HYDROCARBON INTRODUCTION AT A TEMPERATURE ABOVE THAT OFTHE LIQUID HYDROCARBONS AND SUFFICIENTLY HIGH TO SUPPLY THE HEATREQUIRED FOR EFFECTING THE VAPORIZATION AND SAID PARTIAL CONVERSION OFSAID LIQUID HYDROCARBONS, SUPPLYING COOLER SOLID HEAT CARRYING MATERIALTO THE SURFACE OF SAID BED AT A TEMPERATURE CONTROLLED AT A LEVELSUITABLE FOR QUENCHING THE CONVERSION REACTION AND FOR CONDENSING SOMEBUT ONLY A SMALL PORTION OF SAID GASIFORMPRODUCT, PASSING SAID GASIFORMPRODUCT CONTAINING ENTRAINED LIQUID UPWARDLY THROUGH SAID BED TO CONTACTSAID COOLER SOLID MATERIAL WHEREBY THE CONVERSION REACTION ISSUBSTANTIALLY INHIBITED AND A SMALL PORTION OF THE GASIFORM PRODUCT ISCONDENSED AND DEPOSITED UPON THE SOLID MATERIAL ALONG WITH SAIDENTRAINED LIQUID, WITHDRAWING THE GASIFORM PRODUCT FROM THE UPPERSECTION OF SAID ZONE AND PASSING IT INTO CONTACT WITH A FINELY DIVIDEDADSORBENT CATALYST UNDER CONDITIONS OF TEMPERATURE AND PRESSURE SUITABLEFOR EFFECTING FURTHER CONVERSION TO GASIFORM, GASOLINE CONTAININGPRODUCTS.